The present invention is generally directed to toner compositions, and more specifically the present invention is directed to imaging and printing processes with toner compositions, including magnetic, single component, and two component developer compositions. These compositions are particularly useful for generating documents such as personal checks which are subsequently processed in reader/sorters. In one embodiment of the present invention, there are provided processes for generating documents, such as checks, including for example dividend checks, turn around documents such as invoice statements like those submitted to customers by American Express and VISA, corporate checks, highway tickets, rebate checks, other documents with magnetic codes thereon, and the like, with no toner smearing, or wherein toner smearing is substantially minimized. More specifically, in one embodiment the process of the present invention is accomplished with toner and developer compositions containing, especially as external additives, fluorocarbons, such as Teflon.RTM. and Kynar.RTM., and wherein image smearing and offsetting of the toner to read and write heads, including offsetting to the protective foil that may be present on the aforesaid heads in magnetic ink character recognition processes and apparatus inclusive of, for example, the read and write heads present in MICR (magnetic ink character recognition) reader/sorters such as the commercially available IBM 3890.TM.NCR 6780.TM. reader/sorters from Burroughs Corporation, and the like is minimized, or avoided. Some of the reader/sorter printers contain protective foils thereon, reference for example the IBM 3890.TM., and the problems associated with such protective foils with respect to read and write heads with no foils are alleviated with the processes of the present invention. With the processes utilizing the toner and developer compositions illustrated, the problems of image smearing to, and offsetting from the read and write heads in magnetic ink character recognition apparatuses is substantially eliminated. Moreover, in another embodiment the present invention is directed to improved economical processes for generating documents such as personal checks suitable for magnetic image character recognition wherein image smearing and toner offsetting, including offsetting to read and/or write heads including those with protective foils thereon, or unprotected heads is avoided when such documents are processed in the aforementioned reader/sorters. Furthermore, in another embodiment of the present invention there is provided a process for applying to developed images subsequent to, or simultaneously with fusing, especially magnetic ink developed images such as personal checks, a layer of fluorocarbon additives; and wherein image smearing to, and offsetting from the read and write heads in magnetic ink character recognition apparatuses is substantially eliminated. The toner compositions selected for the process of the present invention in an embodiment are comprised of resin particles, pigment particles, including magnetic components such as magnetites and fluorocarbons as internal, or external additives. There is also provided in accordance with the present invention processes with positively or negatively charged toner compositions comprised of resin particles, pigment particles, fluorocarbons, and charge enhancing additives. In addition, the present invention is directed to processes with developer compositions comprised of the aforementioned toners and carrier particles. Further, the processes of the present invention with the toner and developer compositions illustrated, including single component toners, enable reliable output copy quality and stable triboelectric charging properties for the toner compositions selected.
Although it is not desired to be limited by theory, toner offset is eliminated, or minimized with the toners, developers, and processes of the present invention, it is believed, because of the presence of the fluorocarbon additives, which additives are free of objectionable odor during fusing, and do not cause undesirable fuser roll contamination as is the situation with some wax components. Offset results from, for example, the developed toner image being removed from the MICR (magnetic ink character recognition) document, such as a check to the read and/or write heads contained in MICR readers, such as the IBM 3890.TM. and the NCR 6780.TM.. When the aforesaid offset is eliminated or substantially reduced, the problem of image smearing onto the MICR documents, such as personal checks, is also avoided or minimized. Apparently, although it is not desired to be limited by theory the fluorocarbon additive functions as a lubricant against offset. By offset is meant, for example, that the toner is undesirably released from the document, such as personal checks, and transfers and sticks to the aforementioned read and/or write heads. As a result, toner is removed from the checks, or other documents primarily in a continuous manner causing image smearing, and substantially preventing the characters on the checks from being read magnetically and thus rejected in most instances. With the toners, developers and processes of the present invention, these problems are avoided or minimized, and more specifically the reject rate is less than one half of 1 percent for 5,000 checks processed through, for example in the aforesaid IBM 3890.TM. reader/sorter, 10 times in an embodiment of the present invention. With the processes and compositions of the present invention, in an embodiment thereof the reject rate is less than one half of 1 percent, it being noted that an acceptable reject rate usually does not exceed one half of 1 percent (0.5 percent) as determined by the American National Standards Institute (ANSI). Typically, the reject rate with the toners, developers, and processes of the present invention is from about 0 to about 0.3 percent depending, for example, on the sorter set up conditions as contrasted to a reject rate in excess of one half of 1 percent, which is not acceptable, with processes utilizing toner and developer compositions that contain, for example, no additives or other ineffective additives. With toner build up on the read/write heads, the excess toner is released to the check document being processed causing image smearing, which is avoided with the processes of the present invention.
With further respect to the present invention, the process is particularly applicable to the generation of documents including personal checks, which have been fused with soft roll fusers. Fuser rolls such as silicone rolls or other conformable fuser rolls, reference for example the soft fuser rolls incorporated into the Xerox Corporation 4040.TM. machine, are particularly useful with the toners, developers, and processes of the present invention.
The documents, including the personal checks mentioned herein, can be obtained, for example, by generating a latent image thereon and subsequently developing the image, reference U.S. Pat. No. 4,517,268, the disclosure of which is totally incorporated herein by reference, with the toner and developer compositions illustrated herein. The developed image that has been created, for example, in the Xerox Corporation 9700.TM. MICR printer, reference the aforesaid '268 patent, contains thereon, for example, the characters zero, 1, 2, 3, 4, 5, 6, 7, 8 and 9, and up to four symbols (E-13B and CMC-7 font), which characters are magnetically readable by the IBM 3890.TM., or other similar apparatus. One of the problems avoided with the processes of the present invention is to eliminate or reduce the offsetting of the toner as indicated herein to the read and write heads in the apparatus selected for this purpose such as the IBM 3890.TM..
Processes for eliminating or minimizing image smearing in MICR processes are illustrated in U.S. Pat. No. 4,859,550, the disclosure of which is totally incorporated herein by reference. More specifically, there are illustrated in this patent processes for generating documents, which comprise the formation of images, such as latent images, with a printing device especially devices generating from about 8 to about 135 prints per minutef developed the image with a single, or two component developer composition (toner plus carrier), which compositions contain, for example, resin particles, magnetite particles, low molecular weight hydrocarbons with functional groups, or polymeric alcohols; subsequently transferring the developed image to a suitable substrate; permanently affixing the image thereto; and thereafter processing the documents in reader/sorters wherein image offsetting and image smearing are avoided or substantially reduced. Some examples of the aforementioned process wherein a toner with no hydrocarbon, or polymeric alcohol additive is selected as illustrated in U.S. Pat. No. 4,517,268, the disclosure of which is totally incorporated herein, especially column 3. Examples of high speed electronic printing devices disclosed in the aforementioned patent, which devices can also be utilized for the process of the present invention, include the 8700.TM., and 9700.TM. MICR printers available from Xerox Corporation. More specifically, there can be selected for the generation of the documents with magnetic characters thereon the Xerox Corporation 9700.TM. MICR printer, about 120 prints per minute, the Xerox Corporation 8700.TM. MICR printer, about 80 prints per minute, and the like. Some disadvantages associated with the polymeric alcohols and other additives of the aforementioned '550 patent, which disadvantages are avoided and/or minimized with the present invention, include objectionable odor during fusing, fuser roll contamination, and/or limited fuser roll life.
Developer and toner compositions with certain waxes therein are known. For example, there are disclosed in U.K. Patent Publication 1,442,835 toner compositions containing resin particles and polyalkylene compounds, such as polyethylene and polypropylene of a molecular weight of from about 1,500 to 6,000, reference page 3, lines 97 to 119, which compositions prevent toner offsetting in electrostatic imaging processes. Additionally, the '835 publication discloses the addition of paraffin waxes together with, or without a metal salt of a fatty acid, reference page 2, lines 55 to 58. In addition, many patents disclose the use of metal salts of fatty acids for incorporation into toner compositions, such as U.S. Pat. No. 3,655,374. Also, it is known that the aforementioned toner compositions with metal salts of fatty acids can be selected for electrostatic imaging methods wherein blade cleaning of the photoreceptor is accomplished, reference U.S. Pat. No. 3,635,704, issued Jan. 18, 1972, the disclosure of which is totally incorporated herein by reference. Additionally, there are illustrated in U.S. Pat. No. 3,983,045 three component developer compositions comprising toner particles, a friction reducing material, and a finely divided nonsmearable abrasive material, reference column 4, begining at line 31. Examples of friction reducing materials include saturated or unsaturated, substituted or unsubstituted, fatty acids preferably of from 8 to 35 carbon atoms, or metal salts of such fatty acids; fatty alcohols corresponding to said acids; mono and polyhydric alcohol esters of said acids and corresponding amides; polyethylene glycols and methoxy-polyethylene glycols; terephthalic acids; and the like, reference column 7, lines 13 to 43.
In a patentability search report, the following U.S. patents were recited: U.S. Pat. No. 4,517,268, the disclosure of which is totally incorporated herein by reference which illustrates xerography to print MICR legends, and more specifically describes a MICR process wherein the developer is comprised of a toner of magnetite and resin, and the carrier is comprised of ferrite cores; also note column 3, beginning at around line 15, wherein it is indicated that the process of the '268 patent in one embodiment involves the generation of documents including personal checks, which documents are suitable for magnetic image character recognition and wherein conventional electrostatographic methods are selected and wherein the magnetic toner composition contains from about 20 percent by weight to about 70 percent by weight of various magnetites and 30 to 80 percent of certain toner resin particles; and also note the disclosure in column 5, beginning at line 10 wherein developer compositions are formulated; U.S. Pat. No. 4,268,598, the disclosure of which is totally incorporated herein by reference, which discloses a developer comprised of toner powder particles and a fluoroaliphatic sulfonamido surface active material, which developers may be selected for printing tickets, and the like, reference column 10 for example; also note column 7, wherein both pressure fixable and heat fusible toners may be employed, preferably conductive and magnetically attractable; U.S. Pat. No. 4,339,518, the disclosure of which is totally incorporated herein by reference, which discloses the incorporation of fluorine containing resins in a toner that will form a xerographic print that can be selected as a printing master; also note column 4, beginning at around line 16, wherein the dielectric toner contains a particular flow reading containing resin in an amount of at least 0.5 percent by weight calculated as fluorine, and that the fluorine containing resin has an excellent frictional charging property, a low surface energy, and excellent lubricating property with examples of the fluorine containing resins being outlined in column 4, beginning at around line 40, and the preparation of dielectric toner wherein the fluorine is incorporated into the toner composition is outlined in column 6, beginning at line 26; U.S. Pat. No. 4,388,396, the disclosure of which is totally incorporated herein by reference, which discloses magnetic toners with incorporated fluorocarbons as offset preventing agents; also disclosed, reference column 3, are developers including one component type developers comprising particles in which a fine powder of a magnetic substance has been incorporated therein with examples of aliphatic fluorocarbons being illustrated in column 4, beginning at around line 18, and examples of magnetites being outlined in column 9, beginning at around line 36; further, note that the fluorocarbon is incorporated into the toner, and note the disclosure beginning in column 10, line 25; U.S. Pat. No. 4,560,635 relating to magnetic toners wherein, for example, vinylidnene fluoride can be selected as a resin; U.S. Pat. No. 4,590,142 relating to the use of polytetrafluoroethylene as a lubricant for magnetic toners; and as background or collateral interest U.S. Pat. Nos. 3,778,262; 3,977,871; 4,002,570 and 4,051,077.
Described in U.S. Pat. No. 4,367,275 are methods of preventing offsetting of electrostatic images of the toner composition to the fuser roll, which toner subsequently offsets to supporting substrates such as papers wherein there are selected toner compositions containing specific external lubricants including various waxes, see column 5, lines 32 to 45, which waxes are substantially different in their properties and characteristics than the additives selected for the toner and developer compositions of the present invention; and moreover, the toner compositions of the present invention with the aforementioned fluorocarbon additives possess advantages, such as elimination of toner spotting, not achievable with the toner and developer compositions of the '275 patent.
In U.S. Pat. No. 4,883,736, the disclosure of which is totally incorporated herein by reference, are illustrated toner compositions including magnetic single component, and colored toner compositions containing certain polymeric alcohol waxes. More specifically, there is disclosed in this patent the elimination of toner spots or comets with developer compositions comprised of toner compositions containing resin particles, particularly styrene butadiene resins, pigment particles such as magnetites, carbon blacks or mixtures thereof, polymeric hydroxy waxes available from Petrolite, which waxes can be incorporated into the toner compositions as internal additives or may be present as external components; and optional charge enhancing additives, particularly, for example, distearyl dimethyl ammonium methyl sulfate, reference U.S. Pat. No. 4,560,635, the disclosure of which is totally incorporated herein by reference, and carrier particles. As preferred carrier components for the aforementioned compositions, there are selected steel or ferrite materials, particularly with a polymeric coating thereover, including the coatings as illustrated in U.S. Ser. No. 751,922, (now abandoned) entitled Developer Composition with Specific Carrier Particles, the disclosure of which is totally incorporated herein by reference. One particularly preferred coating illustrated in the aforementioned copending application is comprised of a copolymer of vinyl chloride and trifluorochloroethylene with conductive substances dispersed in the polymeric coating inclusive of, for example, carbon black. One embodiment disclosed in the aforementioned copending application is a developer composition comprised of styrene butadiene copolymer resin particles, and charge enhancing additives selected from the group consisting of alkyl pyridinium halides, ammonium sulfates, and organic sulfate or sulfonate compositions; and carrier particles comprised of a core with a coating of vinyl copolymers, or vinyl homopolymers. The polymeric components of the aforesaid copending application are also selected for various embodiments of the present invention as illustrated herein.
In a Petrolite, Inc. brochure dated 1985, there are disclosed polymeric hydroxy waxes, which brochure indicates that the waxes may have utility as toner.
Moreover, toner and developer compositions containing charge enhancing additives, especially additives which impart a positive charge to the toner resin, are well know. Thus, for example, there is described in U.S. Pat. No. 3,893,935 the use of certain quaternary ammonium salts (R.sub.4 N)+X- as charge control agents for electrostatic toner compositions. There are also described in U.S. Pat. No. 2,986,521 reversal developer compositions comprised of toner resin particles coated with finely divided colloidal silica. According to the disclosure of this patent, the development of images on negatively charged surfaces is accomplished by applying a developer composition having a positively charged triboelectric relationship with respect to the colloidal silica. Further, there is illustrated in U.S. Pat. No. 4,338,390, the disclosure of which is totally incorporated herein by reference, developer and toner compositions having incorporated therein as charge enhancing additives organic sulfate and sulfonate compositions; and in U.S. Pat. No. 4,298,672, the disclosure of which is totally incorporated herein by reference, positively charged toner compositions containing resin particles and pigment particles, and as a charge enhancing additive alkyl pyridinium compounds, inclusive of cetyl pyridinium chloride.
Other prior art disclosing positively charged toner compositions with charge enhancing additives include U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014 and 4,394,430.
Although the above described toner and developer compositions are useful for their intended purposes, there is a need for improved compositions. More specifically, there is a need for toners, developers, and processes enabling the generation of documents such as personal checks, wherein toner offsetting and image smearing is avoided. There is also a need for the generation of developed images including the generation of personal checks in laser printers utilizing magnetic ink character recognition technology, wherein toner offset to protective foils present on the read and write heads is avoided, and image smearing is eliminated or minimized by adding to the toner, as an internal or external additive, fluorocarbons. In addition, there is a need for MICR processes for generating documents, such as personal checks, with toner and developer compositions that maintain their triboelectrical characteristics for extended time periods exceeding, for example, 500,000 developed images. In addition, there is a need for MICR processes with toner and developer compositions wherein toner offsetting to protective foils, and image smearing on documents generated is reduced or eliminated. Furthermore, there is a need for processes wherein image smearing and offsetting is avoided by, for example, applying to the developed image, subsequent to or during fusing, a layer of fluorocarbon additives.